MECHANISM OF THE PHOTOCHEMICAL DEHYDROGENATION AND TRANSFER-DEHYDROGENATION OF ALKANES CATALYZED BY TRANS-RH(PME3)2(CO)CL

被引：64

作者：

MAGUIRE, JA ^{[1
]}

BOESE, WT ^{[1
]}

GOLDMAN, ME ^{[1
]}

GOLDMAN, AS ^{[1
]}

机构：

[1] RUTGERS STATE UNIV,DEPT CHEM,NEW BRUNSWICK,NJ 08903

来源：

COORDINATION CHEMISTRY REVIEWS | 1990年 / 97卷

关键词：

D O I：

10.1016/0010-8545(90)80088-B

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Rh(PMe3)2(CO)Cl catalyzes the photochemical dehydrogenation of alkanes to yield alkenes. H2 is evolved or, in the presence of potential hydrogen acceptors such as t-butylethylene and styrene, hydrogen can be transferred to the olefins. The photokinetics and selectivity of the dehydrogenation reactions have been investigated. Both reactions proceed via a single photochemical step, photoextrusion of carbon monoxide from Rh(PMe3)2(CO)Cl. Study of the transfer-dehydrogenation, particularly of the product ratio (H2 : hydrogenated acceptor), reveals aspects of the dehydrogenation mechanism including steps subsequent to the turnover-limiting step. © 1990.

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页码：179 / 192

页数：14

相关论文

共 43 条

[1] THE ACTIVATION OF C-H BONDS IN CYCLOPENTANE BY BIS(PHOSPHINE)RHENIUM HEPTAHYDRIDES [J].

BAUDRY, D ;

EPHRITIKHINE, M ;

FELKIN, H .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1980, (24) :1243-1244

[2] ACTIVATION OF ALKANES WITH ORGANOTRANSITION METAL-COMPLEXES [J].

BERGMAN, RG .

SCIENCE, 1984, 223 (4639) :902-908

[3] ELECTRONIC SPECTRAL STUDIES OF PLANAR RHODIUM(I) AND IRIDIUM(I) COMPLEXES CONTAINING PI-ACCEPTOR LIGANDS [J].

BRADY, R ;

FLYNN, BR ;

GEOFFROY, GL ;

GRAY, HB ;

PEONE, J ;

VASKA, L .

INORGANIC CHEMISTRY, 1976, 15 (07) :1485-1488

[4] SELECTIVE STOICHIOMETRIC AND CATALYTIC C-H-BOND CLEAVAGE REACTIONS IN HYDROCARBONS BY IRIDIUM COMPLEXES [J].

BURK, MJ ;

CRABTREE, RH ;

PARNELL, CP ;

URIARTE, RJ .

ORGANOMETALLICS, 1984, 3 (05) :816-817

[5] THERMAL AND PHOTOCHEMICAL CATALYTIC DEHYDROGENATION OF ALKANES WITH [IRH2(CF3CO2)(PR3)2] (R = C6H4F-P AND CYCLOHEXYL) [J].

BURK, MJ ;

CRABTREE, RH ;

MCGRATH, DV .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (24) :1829-1830

[6] SELECTIVE CATALYTIC DEHYDROGENATION OF ALKANES TO ALKENES [J].

BURK, MJ ;

CRABTREE, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (26) :8025-8032

[7]

CALVERT JG, 1966, PHOTOCHEMISTRY, P170

[8] ACTIVATION OF C-H BONDS IN SATURATED-HYDROCARBONS - H-D EXCHANGE BETWEEN METHANE AND BENZENE CATALYZED BY A SOLUBLE IRIDIUM POLYHYDRIDE SYSTEM [J].

CAMERON, CJ ;

FELKIN, H ;

FILLEBEENKHAN, T ;

FORROW, NJ ;

GUITTET, E .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (10) :801-802

[9] THE ORGANOMETALLIC CHEMISTRY OF ALKANES [J].

CRABTREE, RH .

CHEMICAL REVIEWS, 1985, 85 (04) :245-269

[10] SOME IRIDIUM HYDRIDE AND TETRAHYDROBORATE COMPLEXES WITH BULKY TERTIARY PHOSPHINE LIGANDS [J].

EMPSALL, HD ;

HYDE, EM ;

MENTZER, E ;

SHAW, BL ;

UTTLEY, MF .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1976, (20) :2069-2074

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